Multi-color coating compositions and methods of preparation thereof



United States Patent 3,185,653 MULTi-COLOR COATING COMPOSITIONS AND MLETHODS OF PREPARATION THEREOF Karen Eistrup Knudsen, Allerod, Denmark, assignor to Far-veog Lakfabriken s n m & (30., Aktieselskah, Soborg, Denmark, a Danish company No Drawing. Filed July 10, 1962 Ser. No. 208,920 Claims priority, application Denmark, Jan. 18, 1958, 163/ 1958 14 Claims. (Cl. 260- -4) This application is a continuation-inpart of Serial Number 777,824, filed December 3, 1958, now abandoned.

This invention relates to coating compositions and methods of preparing such compositions. More particularly the invention is concerned with stable, liquid oil-in-water type emulsion coating compositions containing pigmented globules adapted to produce a spotted color effect when applied to a surface.

Usually coating compositions of the kind concerned are multicolor-coating compositions comprising globules of at least two different colors, but coating compositions comprising globules of only one color may also be used for producing a coating film having colored stains to be seen against the original color of the surface treated.

It was found that known multi-color coating compositions suffer amongst others from the drawback that they can only be used with difliculty as a coating applied by brush to floors and Walls without having the different colors run into each other. Although the known coating compositions may be applied by means of spraying this is very often disadvantageous indoors.

It is known to prepare a multi-color coating composition consisting of an external phase into which two or more oilpaints are dispersed in conventional manner as internal phases, said external phase serving for separating the different colored globules of the dispersion. In these known compositions said external phase consists of an aqueous solution of casein with an addition of alcohol, acetone or both. However, such a multi-color coating composition can only be applied by dipping or spraying. If applied by means of a brush or the like the hairs of the brush will break the globules in the composition and cause intermixing of the colors so that the intended separation of the colors from each other cannot be obtained. Further this known multi-color coating composition cannot be stored for a long period because the different colored globules of the dispersion settle so thatbefore use stirring is necessary and such a stirring causes the globules to break and thereby causes an inter-mixing of the different colors.

It is also known to prepare a color coating composition by dispersion of one, two or more conventional oil based or synthetic based paints in water to which is added a colloidal stabilizing agent such as gums, cellulose derivates, carbohydrates, water soluble synthetic organic materials or colloidal inorganic materials. When applied to a surface by means of spraying such a coating composition forms a film consisting of a very great number of small colored particles each adhering to the surface or to another particle and further bound together by the stabilizing agent. However, only coating compositions of this kind having only one color are able to be applied by brush because the surface layer of the colored globules is easily broken by the hairs of the brush so that in case of a multi-color coating composition of said kind, when applied to a surface by brush the different colors will run into each other.

Still other, bi-color coating compositions are known consisting of an unstable emulsion of two different colored phases, an internal phase being of aqueous nature, and containing cellulose-containing fibre materials Patented May 25, 1965 and an external phase being of non-aqueous nature. When such a coating composition is applied to a wall, a wallpaper-like coating patterned in two colors with an appearance similar to paper is obtained. This effect is due to the presence of cellulose-containing fibres to protect the globules of the emulsion so that the coating composition may be applied by brush. One the other hand, such a coating composition can only be used when a wallpaper-like coating is wanted. Further, this emulsion is unstable, and the coating composition can be stored only for a very short time.

A well known type of coating composition is the socalled emulsion paints. Such a paint consists of an emulsion of a disperse phase in a continuous'aqueous phase, which disperse phase as binder comprises polymeric materials, preferably of polystyrene type, styrene-butadiene type, poly(vinyl acetate) type and polyacrylic type, conf. for example Encyclopedia of Chemical Technology, First Supplement Volume, The Interscience Encyclopedia, Inc., New York, 1957.

When such an emulsion paint is applied to a surface by means of spraying, by brush, or in another way the water will evaporate and the particles of the disperse phase will coalesce to form a continuous film.

Coating compositions are also known in which cyclized rubber is used as binder, confl for example Henry Fleming Payne, Organic Coating Technology, volume I, John Wiley & Sons, Inc., New York, 1954; Paint and Varnish Production, January-May 1959; and the US. patent specification No. 2,661,340 of G. J. van Veersen. In such coating compositions the cyclized rubber is used dissolved in a hydrocarbon solvent and when the coating composition is applied to a surface the solvent evaporates and a glossy film which hardens on exposure to air is obtained.

An object of my invention is to provide a stable, liquid oil-in-water type emulsion coating composition containing pigmented globules adapted to produce a spotted color effect and especially adapted to be applied to a surface by brushing without rupture of the said globules by the hair of the brush.

Another object of my invention is to provide such a coating composition which is stable when stored.

Another object of the invention is to provide a multicolor coating composition by which it is possible, when it is applied by brush, depending on the manner in which the brush is manipulated during the application, to obtain different patterns formed by one color or by two or more colors together on a background formed by a further color.

A further object of the invention is to provide a stable liquid oil-in-Water type emulsion coating composition containing unpigmented as well as pigmented globules, the second said globules having the same or different colors and being adapted-especially when applied by brush-to provide 9. spotted color effect without rupture of the second said globules bythe hair of the brush and without possible diiferent colored globules of said second kind coalescing, so that a coating is obtained .having a film produced by the uncolored globules under or in which the color or the different colors of the second said globules remain as discrete and distinguishable spots after the coating film has hardened.

coatings of uniform appearance on surfaces of different kinds.

A further object of my invention is to provide a method of preparing a coating composition of the kind stated above.

These and many other objects and advantages of my invention will appear from the following description.

My invention is based on the discovery that a useful emulsion coating composition overcoming the above disadvantages by the known coating compositions adapted to produce spotted color efifects may be obtained when a coating composition having a binder consisting of a solution of cyclized rubber in a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphaticand aromatic hydrocarbons is emulgated in an emulsion'paint in which further a hydrocarbon solvent of the same group is emulgated, provided said emulsion coating composition, further comprises a colloidal stabilizing agent. I have found that in such an emulsion coating composition a powerful protection of the surface layers of the single emulsified globules of the cyclized rubber coating composition is achieved so that when the composition is applied to a surface by means of a brush said surface layers are not broken by the hairs of the brush or at least not until the globules are fixed to the surface, but are extended to form oblong colored spots or stains incorporated in a film formed by the emulsion paint which latter can be pigmented and thereby colored or unpigmented and thereby colorless. In the first said case the globules form colored spots seen on the background of the color of the emulsion paint, in the last said case the colored globules form colored spots seen on the background of the original color of the surface. It has to be noted that'the globules of the emulsion paint are not protected so that these globules will as in conventional emulsion paints coalesce when the emulsion coating composition is applied to a surface.

In accordance herewith, an important feature of my new coating composition is that it comprises a stable emulsion of at least two dispersed phases in a continuous aqueous phase of said emulsion, one of said two dispersed phases comprising a solution of cyclized rubber in at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, coloring pigment being incorporated in said solution of cyclized rubber; the second of said two dispersed phases comprising emulsified synthetic polymeric material; at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons being further emulgated in said continuous aqueous phase; said emulsion coating composition further comprising a colloidal stabilizing agent.

When it is necessary that the continuous aqueous phase included a phase comprising a hydrocarbon solvent this is owing thereto that otherwise the continuous aqueous phase alone as Well as together with the second dispersed phase has a tendency to draw the hydrocarbon solvent out of the dispersed phase or phases comprising a solution of cyclized rubber which results in a hardening the surface of the globules of said last named phase and the coating composition becomes unusable. This tendency is eliminated, however, when a hydrocarbon solvent is emulgated in the continuous aqueous phase.

The quantity of hydrocarbon solvent emulsified in the continuous aqueous phase lies between 2% and 60% by are obtained by using polymeric material of the polyacrylic type or of the styrene-butadiene type.

To secure stability of my new coating composition and to facilitate the manufacture of the same, as stated above it is necessary that it contains a colloidal stabilizing agent. Many different kinds of such stabilizing agents are usable, but I have found it most advantageous to use as colloidal stabilizing agent a salt, preferably an alkali salt of polyacrylic acid, for example ammonium polyacrylate or sodium polyacrylate. As further examples of colloidal stabilizing agent which advantageously may be used, methyl cellulose, carboxy-methyl-cellulose, alginates,

w and tragacanths are mentioned.

weight, preferably between 5% and 15% by weight of By use of the coating composition according to my invention it is possible by application of the composition on a surface by means of a paint brush to obtain in one coating operation a film showing one or more distinctly separated and different colors scattered over the surface.

In case of a one-color coating composition according to my invention the pigment or pigments necessary for producing the color are incorporated only in the dispersed phase containing cyclized rubber and a coating film is obtained showing a great number of discrete color stains in a colorless coating film.

In case of a multi-color coating composition according to my invention a continuous aqueous phase is used in which pigment or pigments corresponding to the one color is incorporated, and one or more dispersed phases of the first kind are used each having incorporated therein pigment or pigments corresponding to one of the other colors. By application of such a coating composition a coating film is obtained having a uniform base color corresponding to the color of the continuous aqueous phase and a great number of discrete stains of the color of each dispersed phase of the first kind scattered over the base color, the stains being distinctly separated mutually as well as from the base color.

A multi-color coating composition according to my invention may also be obtained wherein a more or less colorless disperse phase is used together with two or more continuous aqueous phases of the first kind, each having incorporated therein pigment or pigments corresponding to each of different colors, to produce a film showing a great number of different colored, discrete spots scattered over the surface.

My invention also relates to a method of preparing my new coating composition.

The greatest difficulty in the manufacture of the present coating composition is to produce the final emulsion since the pigmented solution of cyclized rubber cannot or can at least only with very great difficulty be directly emulsified in the continuous aqueous phase.

However, it has been found that emulsifying of the dispersed phase of the first kind can be successful if this phase is pre-emulsified in a solution (colloidal solution) of colloidal stabilizing agent and only then is emulsified as a phase in a pre-emulsion consisting of the second dispersed phase and the hydrocarbon solvent emulgated in the continuous aqueous phase. By such a pre-emulsifying operation of the dispersed phase of the first kind with an aqueous solution of colloidal stabilizing agent, an unstable emulsion results, but the following emulsifying step using this unstable emulsion with the pre-emulsion of the second dispersed phase in the continuous aqueous phase has been found to result in a stable final emulsion.

It is found that the proportion between the quantity of dispersed phase of the first kind and the quantity of the solution of colloidal stabilizing agent, in which this dispersed phase has to be pre-emulsified, may vary within wide limits. However, extremely good results are obtained when the usually paste-like dispersed phase of the. first kind is pre-emulsified in a quantity by weight of solution of colloidal stabilizing agent approximately equal to the quantity by weight of this phase, for example when parts by weight of such a dispersed phase is preemulsified in 80 to 120 parts by weight of a .5 to 2.5% aqueous solution of colloidal Stabilizing agent.

A further feature of importance for the formation of the final emulsion is the viscosity of the dispersed phase of the first kind before this is added to the continuous phase. If the emulsifying of this dispersed phase in the continuous phase shall be carried through in an easy manner, it is appropriate that before the dispersed phase of the first kind is emulsified in the solution of colloidal stabilizing agent, the viscosity of this dispersed phase is adjusted with hydrocarbon solvent for the cyclized rubber to between 40 secs. and 200 secs. preferably about 105 secs. measured by means of a Stormer viscosimeter with a load of 1000 grams at 20 C. according to ASTM Standard D562.

The viscosity of the pre-emulsion of the second dispersed phase has some, although lesser, importance. Thus it is advisable that before the dispersed phase of the first kind is emulsified in said pre-emulsion, the viscosity of this preemulsion be adjusted to between sees. and 90 secs. preferably to about 45 secs. measured by means of a Stormer viscosimeter with a load of 250 grams at 20 C. according to ASTM Standard D562. This adjustment of the viscosity of said pre-emulsion can be done by means of water.

The emulsifying in the pre-emulsion of the second dispersed phase in the continuous aqueous phase of the above stated further pro-emulsion of dispersed phase of the first kind in a solution of colloidal stabilizing agent is most suitably carried out by pouring the last pro-emulsion into a bulk ofthe first pre-emulsion under very gentle agitatation. If too great an amount of the second pre-emulsion is added to the first pre-emulsion'at a time, there is a dangerof separation of the dispersed phase of the first kind from the continuous phase. Even a too powerful agitation during the emulsifying process has been shown to EXAMPLE 1 Bi-color coating composition providing a white base color with black spots A white emulsion paint is made by mixing:

Parts by weight Water 15.0 Sodium hexamethaphosphate .2 Borax .5 16% aqueous solution of ammonium polyacrylate 1.5

Dolomite 8.0 Micro talc 18.8 Titanium dioxide anatase Q. 20.0

with subsequent homogenizing in a slowly rotating homogenizer, followed by an addition of 35.0 parts by weight of an emulsified polymeric material, such as a 55% aqueous emulsion of acrylic acid methyl-butyl ester copolymer based on 40% methyl acrylate and 60%butyl acrylate and having a mol. wt. of about 1.3-10 for example an emulsion of the kind sold in the trade as Acronal 14D. After stirring, a dispersion or emulsion is obtained in which by quick agitation 12 parts by weight of petroleum spirit is emulsified.

Finally the viscosity of the thus obtained 100 parts of weight of pro-emulsion is adjusted by addition of water to a viscosity of 45 secs. measured on a Stormer viscosimeter with a load of 250 gr. at 20 C. according to ASTM Standard D562.

Further a black paste is made by grinding By adding further amounts of petroleum spirit the viscosity of the paste is adjusted to 105 secs. measured on a Stormer viscosimeter with a load of 1000 grams at 20 C, according to ASTM Standard D562.

30 parts by we ht of his Pa t r hen emu s in 27 parts by weight of a 1% aqueous solution of ammonium polyacrylate by slow stirring. The unstable emulsion obtained is by gentle stirring poured into parts by weight of the white emulsion paint stated above.

A black/white coating composition is obtained having a good storage stability. The paint can be applied on a support, even on a rough or porous support in thick as well as thin coats by means of a paint brush by any other suitable application method resulting in a coating film having a smooth surface. The film will have a white base color on which is scattered a great number of discrete black stains, the pattern of the stains depending mainly on the manner in which the brush or other application device has been manipulated.

EXAMPLE 2 Bi-color coating composition providing a red base color with whitespots 16% aqueous solution of ammonium polyacrylate 2:0 Micro talc 18.8 Red iron oxide V 21.0

with subsequent homogenizing in a slowly rotating homogenizer, and adding to this homogenized mixture 31 parts by weight of'an emulsified polymer, such as a 55% aqueous dispersion of acrylic methyl-butyl ester copolymer (based on 40% methyl acrylate and 60% butyl acrylate, and having a mo. wt. of about 1.4-10 fOIbX- ample an emulsion of the kind sold in the trade as Acronal 14D. After stirring, an emulsion is obtained in which further by vigorous agitation 8 parts by weight of petroleum spirit and 4 parts by weight of vegetable turpentine are emulsified. Finally, the viscosity of the pre-emulsion obtained is by addition of Water adjusted to a viscosity of 45 secs. measured on a Stormer viscosimeter with a load of 250 gr. at 20 C. according to ASTM Standard D562.

Further a paste is made by grinding Parts by weight Titanium dioxide anatase 20.0 Barium oxide 25.0

60% solution of cyclized rubber in petroleum spirit 55.0

poured into 100 parts by weight of the red emulsion paint stated above.

A red/white coating composition is obtained having the same properties as the one stated in Example 1.

EXAMPLE 3 Bi-color coating composition providing a red base color with white spots A red emulsion paint is made by mixing:

with subsequent homogenizing in a slowly rotating homogenizer followed by addition of 35 parts by weight of an emulsified polymer. such as a 46% aqueous dispersion of acrylic acid methylbutyl ester copolymer (based on 30% methyl acrylate and 70% butyl acrylate and having a mol. wt. of about 125-10 for example an emulsion of the kind sold in the trade as Rhoplex AC33. A pro-emulsion is obtained in which 12 parts by weight of petroleum spirit are emulsified by vigorous agitation. The viscosity of the pre-emulsion thus obtained is adjusted by addition of water to a viscosity of 45 secs. measured on a Stormer viscosimeter with a load of 250 gr. at 20 C. according to ASTM Standard D562.

A paste is made by grinding The viscosity of this paste is by addition of turpentine or petroleum spirit adjusted to 105 secs. measured on a Stormer viscosimeter with a lead of 1000 gr. at 20 C. according to ASTM Standard D562.

30 parts by Weight of this paste are emulsified by gentle stirring into 27 parts by weight of a 1% aqueous solu tion of ammonium polyacrylate. An unstable pro-emulsion is obtained which under gentle agitation is poured into 100 parts by weight of the red emulsion paint stated above.

A red/white coating composition is obtained having the same properties as the ones stated in Examples 1 and 2.

EXAMPLE 4 Bi-color coating composition providing a grey base color with green spots are mixed and homogenized in a slowly rotating homogenizer, whereupon 30 parts by weight of an emulsified polymer such as a 55% aqueous dispersion of acrylic acid methyl-butyl ester copolymer (based on 40% methyl acrylate and 60% butyl acrylate and having a mol. wt. of about 1.410 for example an emulsion based on emulsion of the kind sold in the trade as Acronal 14D is added under stirring. A pre-emulsion or dispersion is 8 obtained in which 12 parts by weight of petroleum spirit are emulsified by vigorous agitation.

A paste is made by grinding Parts by weight Chromium oxide hydrate, green 24.0 Dolomite 26.0 60% solution of cyclized rubber in petroleum spirit 50.0

The viscosity of this paste is by addition of turpentine or petroleum spirit adjusted to 105 secs. measured on a Stormer viscosime'ter with a load of 1000 gr. at 20 C. according to ASTM Standard D562.

30 parts by weight of this paste is emulsified by slowly stirring in 27 parts by weight of a 1% aqueous solution of sodium polyacrylate. The unstable pre-emulsion thereby obtained is by gentle stirring poured into parts by weight of the pre-emulsion stated above.

A grey/ green coating composition is obtained having approximately the same properties as the composition according to Examples 1, 2 and 3.

EXAMPLE 5 Bi-color coating composition providing white base with black spots Parts by weight Water 15.6 25% aqueous dispersion of the sodium salt of condensed sulfonic acid (sold in the trade as Tamol 731 (25% .2 Lecithin .2 Mica 5.0 Micro talc 5.0 Titanium dioxide anatase 20.0

are mixed and homogenized in a slowly rotating homogenizer whereupon 40 parts by weight of a 46% aqueous emulsion of styrene butadiene latex with 60% styrene (sold as Dow Latex 512K) are added under stirring. A dispersion is obtained in which by vigorous agitation 14 parts by weight of white spirit is emulsified. In 100 parts by weight of this emulsion 30 parts by weight of the unstable pre-emulsion of black paste and ammonium polyacrylate stated in Example 1 is emulsified under gentle stirring.

A white/black coating composition is obtained having approximately the same properties as the compositions according to the foregoing examples.

EXAMPLE 6 Three-color coating composition providing a grey base color with green and black spots 50 parts by weight of a bi-color coating composition prepared according to Example 1 are by gentle stirring mixed with 50 parts by weight of a biecolor coating composition prepared according to Example 4. A threecolor coating composition is obtained having two groups of globules based on polymeric material and colored white and black, and two groups of globules based on cyclized rubber and colored black and green, all said globules being emulgated in a continuous aqueous phase in which they float independent of each other. When this composition is applied to a surface by means of a brush, the two first said groups of globules will coalesce and form a light grey compound, whereas the two last said groups of globules will remain separated, so that a coating film is obtained having a light grey base color and a great number of discrete black and green stains scat tered thereover in a pattern mainly depending on the manipulation of the brush.

Even coating compositions having more than three colors may be obtained by mixing a suitable number already prepared coating compositions of the kind described each with one or more colors.

It is also possible direct to prepare a multi-color composition of the kind described with two or more dispersed 9 phases of the kind comprising cyclized rubber. To a common pre-emulsion of the dispersed phase of the kind comprising emulgated polymeric material in the continuous'phase there are added simultaneously dispersed phases of the kind comprising cyclized rubber. This mixing has to be carried through very carefully to avoid intermixing and unintended color blending of different parts of the different phases of the last said kind. The simultaneous addition of more such dispersed phases to a common preemulsion may be conveniently carried out in a wide container holding the common pro-emulsion and the different dispersed phases of the last said kind are added at points.

placed at relatively great distance from each other so that each of these phases is mixed with at least some pre-' emulsion before reaching another of these phases.

The terms and expressions which I have employed are used as terms of description and not of limitation, and I have no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof, but recognize that various modifications are possible within the scope of the invention claimed.

I claim:

1. A stable, liquid oil-in-water type emulsion coating composition containing pigmented globules adapted to produce a spotted color effect by brushing on a surface without rupture of the globules by the hair of the brush, which comprises at least two dispersed phases in a continuous aqueous phase of said emulsion; one of said two dispersed phases comprising a solution of cyclized rubber in at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, coloring pigment being incorporated in said solution of cyclized rubber; the second of said two dispersed phases comprising an emulsified synthetic polymeric material; at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons being further emulgated in said continuous aqueous phase; said emulsion coating composition further comprising a colloidal stabilizing agent.

2. A coating composition according to claim 1, in which at least one coloring pigment is incorporated in said second dispersed phase.

3. A stable, liquid oil-in-water type emulsion multicolor coating composition containing pigmented globules adapted to produce a spotted color effect by brushing on a surface without rupture of the globules by the hair of the brush, which comprises a first group of globules and a second group of globules; said first and second group of globules being dispersed in a continuous aqueous phase; at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons being further dispersed in said continuous aqueous phase; said first group of globules comprising globules of different color, each of said globules of said first group containing a pigmented solution of cyclized rubber in at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, each globule of said second group containing an emulsified synthetic polymeric material; said coating composition further comprising a colloidal stabilizing agent.

4. A method of preparing a coating composition comprising a stable emulsion of at least two dispersed phases in a continuous aqueous phase; one of said two dispersed phases comprising a colored solution of cyclized rubber in at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons; the second of said two dispersed phases comprising an emulsified synthetic polymeric material; said method including the steps of emulsifying said second dispersed phase in said continuous aqueous phase, in order to obtain an emulsion component; emulsifying at least one hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hy- 6; A method according to claim 4 in which 100 parts by Weight of said first dispersed phase are emulsified in to 120 parts by weight of said solution of colloidal stabilizing agent for obtaining said second pre-emulsion.

7. A method according to claim 4, in which the hydrocarbon solvent emulsified in said emulsion component amounts to 5 to 15% byweight; of the total composition.

8. A method according to claim 4, including the further step of adjusting by means of a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, the viscosity of said first dispersed phase to between 40 and 20,0 secs. measured on a Stormer viscosimeter with a load of 1000 gr. at 20 C. according to the ASTM Standard D562 before said emulsifying of said first dispersed phase in said solution of colloidal stabilizing agent.

9. A method according to claim 4, including the further step of adjusting by means of a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, the viscosity of said first dispersed phase to a viscosity of about 105 secs. measured on a Stormer viscosimeter with a load of 1000 gr. at 20 C. according to ASTM Standard D562 before said emulsifying of said first dispersed phase in said solution of colloidal stabilizing agent.

10. A method of preparing a coating composition comprising a stable emulsion of at least three dispersed phases in a continuous aqueous phase, a first of said three dispersed phases comprising an emulsified synthetic polymeric material; a second of said dispersed phases comprising a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons; a third of said three dispersed phases comprising a solution of cyclized rubber in a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic, and aromatic hydrocarbons, at least one pigment being incorporated in said solution; said method including the steps of emulsifying said first and said second dispersed phase in said continuous aqueous phase, in order to obtain a first pro-emulsion; adjusting the viscosity of said first pre-emulsion to a viscosity to between 10 and secs. measured on a Stormer viscosimeter with a load of 250 gr. at 20 C. according to ASTM Standard D562; emulsifying said third dispersed phase in a solution of colloidal stabilizing agent, in order to obtain a second pre-emulsion; and emulsifying said second pre-emulsion in said first pre-emulsion.

11. A method according to claim 10, in which the viscosity of said first pre-emulsion is adjusted to a viscosity of about 45 secs.

12. A method of preparing a multi-color coating composition comprising a stable emulsion of two dispersed phases in a continuous aqueous phase having colored pigment incorporated therein, a first of said two dispersed phases comprising an emulsified synthetic polymer; a second of said two dispersed phases comprising a solution of cyclized rubber in a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, at least one pigment being incorporated in said solution; said method including the steps of emulsifying said first dispersed phase, said coloring pigment and a hydrocarbon solvent selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons in said continuous aqueous phase, in order to obtain a first pre-emulsion; adjusting the viscosity of said first pre-emulsion to a viscosity of between 10 and 90 secs.

1 l measured on a Stormer viscosimeter with a load of 250 gr. at 20 C. according to ASTM Standard D562; adjusting the viscosity of said second dispersed phase to a viscosity of between 40 and 200 secs. measured on a Stormer viscosimeter with a load of 1000 gr. at 20 C. according to ASTM Standard D562; emulsifying said second dispersed phase in a solution of a colloidal stabilizing agent, in order to obtain a second pre-emulsion, and emulsifying said second pre-emulsion in said first pre-emulsion by pouring said second pro-emulsion into a bulk of said first pre-emulsion under mild stirring.

13. A method according to claim 12, in which the viscosity of said first pre-emulsion is adjusted by addition of water thereto.

14. Astable, liquid oil-in-water type emulsion coating composition containing pigmented globules adapted to produce a spotted color effect by brushing on a surface without rupture of the said pigmented globules by the hair of the brush, which comprises at least two dispersed phases in a continuous aqueous phase of said emulsion; one of said two dispersed phases comprising a solution of References Cited by the Examiner UNITED STATES PATENTS 4/52 Zola 106--170 12/53- Van Veersen 260-734 MURRAY TILLMAN, Primary Examiner.

WILLIAM H. SHORT, Examiner. 

1. A STABLE, LIQUID OIL-IN-WATER TYPE EMULSION COATING COMPOSITION CONTAINING PIGMENTED GLOBULES ADAPTED TO PRODUCE A SPOTTED COLOR EFFECT BY BRUSHING ON A SURFACE WITHOUT RUPTURE OF THE GLOBULES BY THE HAIR OF THE BRUSH, WHICH COMPRISES AT LEAST TWO DISPERSED PHASES IN A CONTINUOUS AQUEOUS PHASE OF SAID EMULSION; ONE OF SAID TWO DISPERSED PHASES COMPRISING A SOLUTION OF CYCLIZED RUBBER IN AT LEAST ONE HYDROCARBON SOLVENT SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC, CYCLOALIPHATIC AND AROMATIC HYDROCARBONS, COLORING PIGMENT BEING INCORPORATED IN SAID SOLUTION OF CYCLIZED RUBBER; THE SECOND OF SAID TWO DISPERSED PHASES COMPRISING AN EMULSIFIED SYNTHETIC POLYMERIC MATERIAL; AT LEAST ONE HYDROCARBON SOLVENT SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC, CYCLOALIPHATIC AND AROMATIC HHDROCARBONS BEING FURTHER EMULGATED IN SAID CONTINUOUS AQUEOUS PHASE; SAID EMULSION COATING COMPOSITION FURTHER COMPRISING A COLLOIDAL STABILIZING AGENT.
 4. A METHOD OF PREPARING A COATING COMPOSITION COMPRISING A STABLE EMULSION OF AT LEAST TWO DISPERSED PHASES IN A CONTINUOUS AQUEOUS PHASE; ONE OF SAID TWO DISPERSED PHASES COMPRISING A COLORED SOLUTION OF CYCLIZED RUBBER IN AT LEAST ONE HYDROCARBON SOLVENT SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC, CYCLOALIPHATIC AND AROMATIC HYDROCARBONS; THE SECOND OF SAID TWO DISPERSED PHASES COMPRISING AN EMULSIFIED SYNTHETIC POLYMERIC MATERIAL; SAID METHOD INCLUDING THE STEPS OF EMULSIFYING SAID SECOND DISPERSED PHASE IN SAID CONTINUOUS AQUEOUS PHASE, IN ORDER TO OBTAIN AN EMULSION COMPONENT; EMULSIFYING AT LEAST ONE HYDROCARBON SOLVENT SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC, CYCLOALIPHATIC AND AROMATIC HYDROCARBONS IN SAID EMULSION COMPONENT, IN ORDER TO OBTAIN A FIRST PRE-EMULSION; EMULSIFYING SAID FIRST DISPERSED PHASE IN A COLLOIDAL STABILIZING AGENT, IN ORDER TO OBTAIN A SECOND PRE-EMULSION, AND EMULSIFYING SAID SECOND PREEMULSION IN SAID FIRST PRE-EMULSION. 